DE1081887B - Process for the preparation of N- (1, 2, 3, 4-tetrahydro-2-naphthyl) ureas - Google Patents
Process for the preparation of N- (1, 2, 3, 4-tetrahydro-2-naphthyl) ureasInfo
- Publication number
- DE1081887B DE1081887B DEV16085A DEV0016085A DE1081887B DE 1081887 B DE1081887 B DE 1081887B DE V16085 A DEV16085 A DE V16085A DE V0016085 A DEV0016085 A DE V0016085A DE 1081887 B DE1081887 B DE 1081887B
- Authority
- DE
- Germany
- Prior art keywords
- tetrahydro
- naphthyl
- urea
- naphthylamine
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title claims 2
- 235000013877 carbamide Nutrition 0.000 title description 10
- -1 1, 2, 3, 4-tetrahydro-2-naphthyl Chemical group 0.000 title description 9
- 150000003672 ureas Chemical class 0.000 title description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- LCGFVWKNXLRFIF-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalen-2-amine Chemical compound C1=CC=C2CC(N)CCC2=C1 LCGFVWKNXLRFIF-UHFFFAOYSA-N 0.000 claims description 5
- UCUXTGVDWJMHRW-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalen-2-ylurea Chemical compound C1=CC=C2CC(NC(=O)N)CCC2=C1 UCUXTGVDWJMHRW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- JRZGPXSSNPTNMA-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalen-1-amine Chemical compound C1=CC=C2C(N)CCCC2=C1 JRZGPXSSNPTNMA-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAGRKAFMISFKIO-UHFFFAOYSA-N Isolysergic acid Natural products C1=CC(C2=CC(CN(C2C2)C)C(O)=O)=C3C2=CNC3=C1 ZAGRKAFMISFKIO-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- ZAGRKAFMISFKIO-QMTHXVAHSA-N lysergic acid Chemical compound C1=CC(C2=C[C@H](CN([C@@H]2C2)C)C(O)=O)=C3C2=CNC3=C1 ZAGRKAFMISFKIO-QMTHXVAHSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PLSFSIDDNZKALV-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalen-1-ylurea Chemical compound C1=CC=C2C(NC(=O)N)CCCC2=C1 PLSFSIDDNZKALV-UHFFFAOYSA-N 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229960003133 ergot alkaloid Drugs 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
- C07C273/1863—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety from urea
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
- C07C2602/28—Hydrogenated naphthalenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von N-( 1 ,2,3,4-Tetrahydro-2-naphthyl)-harnstoffen Gegenstand der Erfindung ist ein Verfahren zur Herstellung von N-(1 ,2,3,4-Tetrahydro-2-naphthyl) -harnstoff bzw. N-(1,2,3,4 -Tetrahydro -2 -naphthyl) - N' - alkylharnstoffen bzw. N,N'-Bis-(1 ,2,3,4-tetrahydro-2-naphthyl)-harnstoff der allgemeinen Formel in der R ein Wasserstoffatom oder eine Alkylgruppe oder den 1 ,2,3,4-Tetrahydro-2-naphthylrest bedeutet.Process for the production of N- (1, 2,3,4-tetrahydro-2-naphthyl) ureas The invention relates to a process for the production of N- (1, 2,3,4-tetrahydro-2-naphthyl) - urea or N- (1,2,3,4-tetrahydro-2-naphthyl) - N '- alkylureas or N, N'-bis (1, 2,3,4-tetrahydro-2-naphthyl) - urea of the general formula in which R is a hydrogen atom or an alkyl group or the 1,2,3,4-tetrahydro-2-naphthyl radical.
Es ist bekannt, daß man monoalkylierte oder dialkylierte Harnstoffe durch Umsetzung von Harnstoff mit primären Alkylaminen oder ihren Salzen erhält. Es ist auch bekannt, daß diese Synthese bei erhöhten Temperaturen durch Konkurrenzreaktionen gestört werden kann, wobei Harnstoff in Biuret übergeht und sich somit der gewünschten Umsetzung entzieht. Insbesondere kann man mit einem solchen andersartigen Verlauf derartiger Reaktionen rechnen, wenn man die Verfahrensweise von .«den innerhalb dieser Umsetzung hinreichend bearbeiteten einfachen niederen Alkylaminen auf höhere primäre Amine ausweitet. It is known that monoalkylated or dialkylated ureas can be used obtained by reacting urea with primary alkylamines or their salts. It is also known that this synthesis can be carried out at elevated temperatures by competitive reactions can be disturbed, whereby urea turns into biuret and thus becomes the desired Implementation withdraws. In particular, one can with such a different course such reactions are to be expected if one follows the procedure of the within simple lower alkylamines to higher ones primary amines.
Ein solches Amin liegt in dem in jüngster Zeit als Zwischenprodukt der Arzneimittelsynthese interessierenden Tetrahydronaphthylamin vor, welches man als ein Bruchstück der natürlichen Mutterkornalkaloide und der Lysergsäure auffassen kann: Lysergsäure Tetrahydronaphthylamin Auf Grund seines sterischen Aufbaus sowie seiner bekannten chemischen Eigenschaften, die insbesondere in seiner Neigung zur Reaktion mit ß-Naphthylamin (das durch Hitzedehydrierung von 1,2, 3,4-Tetrahydro-2-naphthylamin unter den gegebenen Reaktionsbedingungen mit entstehen kann) nach folgender Gleichung: ß-Naphthylamin t 1,2,3,4-Tetrahydro-2-naphthylamin 2 Dihydro-2-naphthylamin und in seiner Oxydationsempfindlichkeit bestehen, war nicht von vornherein zu erwarten, daß die Umsetzung dieses Amins mit Harnstoff oder Monoalkylharnstoffen zur Herstellung von entsprechenden Tetrahydronaphthylharnstoffen einen befriedigenden Verlauf nehmen würde.Such an amine is found in tetrahydronaphthylamine, which has recently been of interest as an intermediate in drug synthesis, which can be viewed as a fragment of the natural ergot alkaloids and lysergic acid: Lysergic acid tetrahydronaphthylamine Due to its steric structure and its well-known chemical properties, which are particularly evident in its tendency to react with ß-naphthylamine (which can also be formed by heat dehydrogenation of 1,2, 3,4-tetrahydro-2-naphthylamine under the given reaction conditions) according to the following equation: ß-naphthylamine t 1,2,3,4-tetrahydro-2-naphthylamine 2 dihydro-2-naphthylamine and its sensitivity to oxidation, it was not to be expected from the outset that the reaction of this amine with urea or monoalkylureas to produce the corresponding tetrahydronaphthylureas would proceed satisfactorily.
Es wurde überraschenderweise gefunden, daß mit Hilfe des erfindungsgemäßen Verfahrens nicht nur der Monotetrahydronaphthylharnstoff leicht und in vorzüglicher Ausbeute entsteht, sondern daß sich unter gleichen Bedingungen auch N-monoalkylierte Harnstoffe mit Tetrahydronaphthylamin zu entsprechenden N-Alkyl-N'-tetrahydronaphthylharnstoffen umsetzen lassen und daß selbst unter Steigerung der Temperatur bis auf 180"C der N,N'-Bis-tetrahydronaphthylharnstoff in guten Ausbeuten zugänglich ist. Dies ist um so bemerkenswerter, als bekannt ist, daß bei Temperaturen über 160"C die Biuretbildung aus Harnstoff stark zunimmt. It has surprisingly been found that with the help of the invention Process not only the monotetrahydronaphthylurea easily and in excellent Yield arises, but that N-monoalkylated under the same conditions Urea with tetrahydronaphthylamine to give the corresponding N-alkyl-N'-tetrahydronaphthylureas let convert and that even by increasing the temperature up to 180 "C of the N, N'-bis-tetrahydronaphthylurea is available in good yields. This is all the more remarkable as it is known that biuret formation occurs at temperatures above 160 "C. from urea increases sharply.
Die nach dem erfindungsgemäßen Verfahren hergestellten Produkte, die bis auf den bereits bekannten Mono-(tetrahydro-2-naphthyl)-harnstoff (G. S chro et er und K. Thomas, Hoppe-Seyler's Zeitschrift für physiologische Chemie, Bd. 110, 1918, S. 273) neue Verbindungen darstellen, sollen als Zwischenprodukte bei der Synthese von Arzneimitteln Verwendung finden. The products manufactured by the process according to the invention, which except for the already known mono- (tetrahydro-2-naphthyl) urea (G. S chro et he and K. Thomas, Hoppe-Seyler's Journal for Physiological Chemistry, Vol. 110, 1918, p. 273) represent new compounds should be used as intermediates in the Synthesis of drugs find use.
Im folgenden werden Beispiele wiedergegeben, die das erfindungsgemäße Verfahren beschreiben: Beispiel 1 N-(1 ,2,3,4-Tetrahydro-2-naphthyl) -harnstoff 20,4g geschmolzener Harnstoff werden unter Stickstoff mit 50 g Tetrahydro-2-naphthylamin versetzt und unter Rühren 7 Stunden auf einer Temperatur vorn 135 bis 1400C gehalten. Die erhaltene Schmelze wird mit Wasser ausgeschüttelt und aus Dioxan umkristallisiert. F. 182 bis 1840 C. Ausbeute: 70 bis 7501o der Theorie. Examples are given below, which the invention Describe method: Example 1 N- (1,2,3,4-tetrahydro-2-naphthyl) urea 20.4 g of molten urea are mixed with 50 g of tetrahydro-2-naphthylamine under nitrogen added and stirred for 7 hours at a temperature from 135 to 1400C held. The melt obtained is shaken out with water and recrystallized from dioxane. F. 182 to 1840 C. Yield: 70 to 75010 of theory.
Beispiel 2 N-(1,2,3,4-Tetrahydro-2-naphthyl)-N'-methylharnstoff 12,8 g geschmolzener Methylharnstoff werden unter Stickstoff mit 25 g frisch destilliertem Tetrahydro-2-naphthylamin unter Rühren 7 Stunden auf einer Temperatur von 120 bis 1250 C gehalten. Anschließend wird die erkaltete Schmelze nach Ausschütteln mit warmem Wasser aus Dioxan umkristallisiert. F. 176 bis 179° C. Ausbeute: 43 bis 49 °/0 der Theorie. Example 2 N- (1,2,3,4-Tetrahydro-2-naphthyl) -N'-methylurea 12.8 g of molten methylurea are mixed with 25 g of freshly distilled under nitrogen Tetrahydro-2-naphthylamine with stirring for 7 hours at a temperature of 120 to Held at 1250 C. The cooled melt is then shaken out with recrystallized from dioxane in warm water. M.p. 176-179 ° C. Yield: 43-49 ° / 0 of theory.
Berechnet: 13a75°/o N; gefunden: 13'980/o N. Calculated: 13a75 ° / o N; found: 13,980 / o N.
Beispiel 3 N,N'-Bis-(1,2,3,4-tetrahydro-2-naphthyl)-harnstoff 10,2 g Harnstoff werden in einer Stickstoffatmosphäre mit 50 g frisch destilliertem Tetrahydro-2-naphthylamin 4 Stunden auf 1800 C erhitzt. Das abgekühlte Reaktions- produkt wird ausDioxan umkristallisiert. F. 260 bis 263° C. Example 3 N, N'-bis (1,2,3,4-tetrahydro-2-naphthyl) urea 10.2 g of urea are mixed with 50 g of freshly distilled tetrahydro-2-naphthylamine in a nitrogen atmosphere Heated to 1800 C for 4 hours. The cooled reaction product is recrystallized from dioxane. F. 260 to 263 ° C.
Ausbeute: 56 bis 62 °/0 der Theorie.Yield: 56 to 62% of theory.
Berechnet: 8,75 0/o N; gefunden: 9,04, 9,05 0/, N. Calculated: 8.75% N; found: 9.04, 9.05 0 /, N.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEV16085A DE1081887B (en) | 1959-03-03 | 1959-03-03 | Process for the preparation of N- (1, 2, 3, 4-tetrahydro-2-naphthyl) ureas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEV16085A DE1081887B (en) | 1959-03-03 | 1959-03-03 | Process for the preparation of N- (1, 2, 3, 4-tetrahydro-2-naphthyl) ureas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1081887B true DE1081887B (en) | 1960-05-19 |
Family
ID=7575425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEV16085A Pending DE1081887B (en) | 1959-03-03 | 1959-03-03 | Process for the preparation of N- (1, 2, 3, 4-tetrahydro-2-naphthyl) ureas |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1081887B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953506A (en) * | 1974-02-07 | 1976-04-27 | American Cyanamid Company | Ureidotetralin compounds |
-
1959
- 1959-03-03 DE DEV16085A patent/DE1081887B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953506A (en) * | 1974-02-07 | 1976-04-27 | American Cyanamid Company | Ureidotetralin compounds |
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